JP2006506316A - Improved fragrance - Google Patents

Abstract

Improved citral derivatives, that have a longer useful shelf life than citral fragrances and flavorings, are disclosed. In one embodiment, the derivatives are prepared by replacing one or more double bonds in citral with a cyclopropyl group, which can be unsubstituted, or substituted with one or two lower alkyl, preferably methyl groups. The alkyl groups can optionally be substituted, for example, with electron donating groups, electron with drawing groups, groups which increase the hydrophilicity or hydrophobocity, and the like. In the derivatives the aldehyde group may be replaced with a nitrile, methyl ether or acetal group. The acetal groups can provide the compounds with a long lasting flavor or fragrance, where the acetals slowly hydrolyze to provide the aldehyde group in citral. Examples of suitable articles of manufacture include candles, air fresheners, perfumes, disinfectant compositions, hypochlorite (bleach) compositions, beverages such as beer and soda, denture cleanser tablets and flavored orally-delivered products such as lozenges, candies, and the like. The derivatives preferably have the structure: <EMI ID=1.1 HE=22 WI=61 LX=576 LY=1907 TI=CF> <PC>wherein Z is O, S, CR 2 or a double or a single bond provided at least one Z is O, S or CR 2 ; and X is a nitrile, methyl ether, or acetal group.

Description

  The present invention relates generally to the field of flavors and fragrances. More specifically, the present invention relates to fragrances and other fragrance articles based on fragrance chemicals that overcome the stability limitations and / or allergy of natural compounds.

  Many fragrances are used in the flavor and fragrance industry. For example, citral has a lemony scent, which is used in many manufactured articles as a flavor and / or fragrance. However, many fragrances contain double bonds, aldehyde groups, and other reactive groups that are potentially susceptible to reactions, resulting in limited useful lifetimes. In addition, many essential oil fragrances have recently been found to cause allergic reactions, making it increasingly difficult to bring such compounds to market.

  Many fragrances that are the basis for the formation of various fragrances are listed on the list of allergenic substances and are banned or restricted in many commercial areas. This prohibition and limitation undoubtedly has a considerable impact on the quality of various fragrances, mainly because the smaller fragrancer palette makes it virtually impossible to create certain notes. Will be affected. Examples of fragrances used to form the Muguere code include hydroxycitronellal, rilal (IFF) lyial, and vojunal. The few remaining Suzuran materials left by the perfumers are cyclamenaldehyde, Hajan and Reimer, Firmenich and the newer Duplica (Quest), Elintal (Quest), Flora hydral ( A more crude fragrance such as florahydr (Givaudan-Roure). Rose Notes also makes it difficult to produce with both geraniol and citronellol on the list, making it difficult to realize many other classic and fantasy notes and themes, and fragrance companies are effectively Thank you for your help.

  It would be desirable to develop derivatives of these compounds that do not cause allergic reactions as well and / or have an improved useful life. Further advantageous properties include improved scent intensity and stability. The present invention provides such fragrances and flavoring agents.

  Disclosed are improved fragrances and flavoring agents in which the fragrance and flavoring agent have a longer shelf life than the parent compound derived therefrom. Specifically, derivatives of fragrances are disclosed that retain the fragrance characteristics of the fragrance and at the same time reduce allergic properties so that the fragrance derivative can have a longer shelf life than the parent compound derived therefrom. Also disclosed are methods of making the derivatives and articles of manufacture containing the derivatives.

  In one embodiment, the parent compound contains one or more double bonds and the derivative substitutes one or more double bonds in the parent molecule with a thioether bond, cyclopropyl group, oxirane group, or thiirane group. It is prepared by. The cyclopropyl group here may be unsubstituted or substituted with one or two lower alkyl, preferably methyl groups. The alkyl group may optionally be substituted with, for example, an electron donating group, an electron withdrawing group, a group that increases hydrophilicity or hydrophobicity, and the like.

  When these parent compounds further contain one or more aldehyde groups, derivatives can be prepared in which at least one aldehyde group in the derivative parent molecule is replaced with a nitrile, methyl ether or acetal group. The acetal group can provide the compound with a long-lasting flavor or fragrance, where the acetal gradually hydrolyzes to provide the parent aldehyde compound. In some embodiments, suitable molecules include both aldehyde and double bond functional groups, both derived as described herein.

  In a third embodiment, the parent compound includes a benzene ring, and derivatives thereof are prepared by replacing the benzene ring with a thiophene ring. The thiophene may preferably contain one or more C1-5 alkyl groups at the 2-position and / or the 3-position. There are a number of known compounds with similar scents where a phenyl group is present in one molecule and an isoprenyl group is present in another molecule. In a fourth embodiment of the invention, the parent compound contains an isobutyl group or a phenyl group, and the derivative is prepared by replacing the isobutyl group or phenyl group with a cyclopropanated isoprenyl group.

  Examples of suitable manufactured articles include candles, indoor deodorants, fragrances, bactericidal compositions, hypochlorite (bleaching) compositions, beverages such as beer and soda, such as US Pat. No. 5,571. , 519 (incorporated herein by reference in its entirety) and flavored oral delivery products such as lozenges, candy and the like.

  Disclosed are improved fragrances and flavoring agents in which the fragrance and flavoring agent have a longer shelf life than the parent compound derived therefrom. This improvement may be in the form of greater strength and / or higher chemical stability that does not change the character of the scent. If greater strength is desired, the fragrance structure is modified without significantly changing the scent characteristics, for example by increasing the zinc binding capacity to increase the scent strength. If higher stability is desired, one or more structural features that affect chemical stability can be changed as described herein without significantly changing scent characteristics.

I. Isodonic molecules The derivatives described herein are isodonic with respect to the compound from which the derivative is derived. Isodonic means “having essentially the same scent profile”. However, while having essentially the same scent profile, the compounds can have improved stability, scent intensity, and / or improved physical and / or chemical properties.

  The compound from which the derivative is derived is a specific fragrance compound present in fragrances, essential oils. Derivatives can be prepared from aromatics or individual compounds, but this is not necessarily so. That is, as long as the final compound is an oil or a derivative of a particular fragrance compound as described herein, the compound can be derived with a synthetic strategy that does not involve the use of fragrance chemicals. All that is required is that the compound is isodonic with the “parent” compound. Isodonic substitutions (eg, ene-cyclopropane substitution, ene-oxirane substitution, ene-thiirane substitution, ene-thioether substitution, isobutyl-phenyl substitution and benzene-thiophene substitution) are described in more detail below. In some embodiments, the parent compound comprises an aldehyde group, a nitrile group, a methyl ether group and / or an ester group in addition to the olefinic phenyl and / or thiophene group. In these embodiments, in addition to the above substitutions, the following additional substitutions can be further made. That is, aldehyde-nitrile substitution, aldehyde-methyl ether substitution, aldehyde-acetal substitution, aldehyde-ester substitution, and the reverse of these substitutions (ie, methyl ether-aldehyde, etc.).

  Replacing the usual chemical features with other features designed to change the chemistry, while leaving the underlying structure intact, and thus substantially independent of the scent, and / or Or stability can be improved. Examples of suitable chemical features to be replaced are described in more detail below.

Double bond substitution and its effect on fragrance Many fragrances contain isoprenyl units and / or other C = C double bonds. The C = C double bond can be substituted with a thioether group, -S-, without significantly changing the scent characteristics. In one embodiment, the carbon double bond is substituted with a thiocyclopropane ring. In this embodiment, sulfur unpaired electrons readily bind to Zn, which increases the intensity of the scent without significantly changing the scent type.

  One or more (if present) C═C double bonds in the essential oil can be replaced with cyclopropane, oxirane (OX) or thiirane (TH) moieties. This substitution keeps the scent of the compound substantially equal, while the scent intensity is dramatically improved. One method of measuring scent intensity is by zinc binding affinity. All the above three-membered rings can be coordinated to zinc ions.

  Another advantage of replacing the C = C double bond with oxirane or thiirane is that it produces a higher molecular weight molecule. Larger molecular weights can reduce the volatility of the molecule, thereby potentially turning the top note into a middle note or the middle note into a dry down note.

  The procedure described herein to improve the fragrance performance is best illustrated by citral. It can be applied directly to any other fragrance with similar structural features, ie C═C double bonds. Citral may be cyclopropanated at one or both of its positions with respect to the two double bonds of the molecule. Thus, there are five CP-mutant forms for citral as shown below, including stereoisomers.

The cyclopropane ring may contain a CH ₂ moiety or may be substituted with one or two methyl groups. The methyl or dimethyl analog has a vibrational spectrum that is more closely matched to citral than the unsubstituted cyclopropane derivative and has a sweeter odor than the unsubstituted cyclopropyl derivative.

  Derivatives described herein include one or both of the double bonds (unsubstituted monoalkyl or dialkyl, which may be substituted or unsubstituted, preferably methyl ) Derivatives substituted with cyclopropyl groups are included. The compound can include substitution of an aldehyde with a methyl ether, nitrile or acetal group in combination with or in place of a cyclopropyl group.

  The synthesis of methyl, dimethyl or unsubstituted cyclopropane derivatives is well known to those skilled in the art, for example, using a bromoform reaction to produce a bromocyclopropane derivative followed by a stoichiometric reaction with methyllithium. Let The aldehyde group is generally protected as an acetal during the reaction and the desired deprotection is performed after the reaction has taken place. However, in one embodiment, the acetal (eg, dimethyl, diethyl, or ethylene glycol) is not deprotected to become an aldehyde, and thus the flavoring or fragrance contains the acetal in part or in whole. The acetal can then gradually hydrolyze over time, releasing a lemon scent / flavor. Alternatively, derivatives containing one or two cyclopropane rings can contain nitrile or methyl ether groups instead of aldehyde groups.

  These simple procedures result in derivatives having a fragrance profile that approximates the fragrance or the individual “parent” compound itself. Further, by substituting the double bond, the labile feature, ie, the double bond is removed, so the derivatives often have greater potential and higher acid and bleach stability.

The same applies to the epoxide (OX) and thiirane (TH) rings. Without counting the mixture of C = C double bond substitutions and stereoisomers, this yields nine possible molecules, even from citral alone, and is a well-known method in the art:
Cyclopropanyl substitution: Simmons-Smith cyclopropanation of aldehydes or corresponding alcohols, followed by periodinane oxidation leading to aldehydes from the latter ¹
Oxiranyl substitution: Epoxidation of m-chloroperbenzoic acid ²
Thianyl substitution: bromination of double bonds on amberlite, followed by S substitution with sodium sulfide ³
Thus, all can be easily obtained by one-step synthesis or two-step synthesis from citral.

In other embodiments, the fragrance chemical comprises an isobutyl group that is substituted with a phenyl group, or vice versa.
¹ Vogel's textbook of practical organic chemistry 5th edition (1989) pp 1106-1108
² Ibid, ppl 127-1129
³ Choi J et al (1995) Bull. Korean. Chem. Soc., 16, 189-190 Convenient Synthesis of Symmetrical Sulfides from Alkyl Halides and Epoxides

Aldehyde substitution with nitrile, methyl ester or acetal groups Many aromatics also contain aldehyde groups. These odorotopes can be prepared by replacing the aldehyde group with a nitrile, methyl ester or acetal group. The conversion of aldehyde groups to nitrile groups is well known in the art and is described, for example, in US Pat. No. 5,892,092. No. 092 teaches a method for producing nitriles from aldehydes. Examples of oximes that are generated from aldehydes and then converted to nitriles include angelica oxime, allepurine oxime, α, β-apocitroneral oxime, bergamoten oxime, pyroturpentine oxime, camphorene oxime, citronellal oxime. , Citral oxime, Chrysantheme oxime, Cyclocitral oxime, Cyclolabangular oxime, Faranar oxime, Farnesal oxime, Isolauran oxime, Ikema oxime, Miltenal oxime, Ferrandrene oxime, Safranal oxime and sorbinal oxime Is included. Specific examples include angelica oxime, bergamoten oxime, cyclolabangular oxime, citral oxime, farnesal oxime, ikema oxime, isolauranal oxime, ferrandrene oxime and sorbinal oxime.

  Acetal formation is well known to those skilled in the art and generally employs the reaction of an aldehyde with an alcohol in the presence of an acid catalyst. Loss of water and acetal is produced. In use, if the acetal is present in an aqueous environment, the acetal can return to the aldehyde, thereby providing a sustained release form of the fragrance.

  Fragrances containing aldehydes further containing one or more double bonds are thioether, (unsubstituted methyl or dimethyl) cyclopropyl, oxirane or thiirane derivatives which also contain nitrile, methyl ether or acetal groups instead of aldehydes Can be converted to

  This method can be applied directly to multiple other classes of fragrances to enhance its potential. Each of the following examples refers to a class of fragrances rather than a single molecule.

  In each case, the C = C double bond can be replaced with CP, OX or TH, resulting in a stronger fragrance with a similar scent profile. Rose oxide is floral, Ionone is woody violet, Damascon is fruity rose, Sandanol is sandalwood, Limonene is woody citrus, Verbion is musk, Linalol is floral-woody and ethyl citronellyl oxalate is musk. Graphs for four of these compounds with CP, OX and TH substitutions are shown in FIGS. 1a-1d. Fig. 1a shows the spectrum of rose oxide, Fig. 1b shows the spectrum of linalool, Fig. 1c shows the spectrum of limonene, and Fig. 1d shows the spectrum of ionone. In each case, the CP, OX and TH substitutions have only a minor effect on the spectrum, ie the scent characteristics.

Benzene-thiophene substitution An additional odd topical replacement is the thiophene ring instead of the benzene ring. For example, when the phenyl rings in lyial, cyclamenaldehyde and boujunal are substituted with thiophene, the vibrational spectra overlap and the new derivative not only has the same scent characteristics, but also enhances the scent intensity. Each of these compounds further comprises an aldehyde group which may be additionally substituted with a nitrile, methyl ether or acetal functional group. Synthetic methods for replacing the phenyl ring in a molecule with a thiophene molecule are well known to those skilled in the art.

  The parent compounds (liliar, cyclamenaldehyde and boujunal) and novel compounds containing thiophene ring substitution are shown below.

  An example of benzene to cyclopropanated isobutyl is the substitution of the phenyl group of 4-methyl-2-phenyl-penten-3-en-1-al with a cyclopropanated isobutyl moiety.

II. Fragrances that can be modified using the chemistry described herein The techniques described herein include fragrances, in particular alcohols related to citral, including lyral, hydroxycitronal and aldehydes, and citronellal, geraniol, nerol, etc. Has a specific use for aromatics. Examples of fragrances that can be modified using the chemistry described herein are listed below and also shown in FIG.

  There are a plurality of fragrance chemicals having aldehyde groups that can be derived using acetals, methyl ethers or nitrile groups using the chemistry described herein. These include, but are not limited to, Angelica, Allepurin, α, β-Apocitronellal, Bergamoten, Pyrotelenne, Camphoren, Citronellal, Citral, Chrysantheme, Cyclocitral, Cyclolavandulal, Faranar, Farnesal, Isolauranal (Isolauranal), Ikema, Miltenal, Ferrandrene, Safranal Oxime and Sorbinal Oxime. Specific examples include angelica, bergamoten, cyclolabangular, citral, farnesal, ikema, isolauranal, ferrandrenandrin oxime and sorbinal oxime.

There are a plurality of aromatics (some of which are listed above) containing olefinic groups derived by forming ene-thioether, ene-cyclopropane, ene-oxirane, and / or ene-thiirane substitutions. . The following are specific fragrances that can be modified as described herein to convert a double bond to an (unsubstituted, methyl or dimethyl) cyclopropyl derivative without significantly changing the scent profile. A fragrance that can be converted and / or that can convert an aldehyde (if present) to an acetal, methyl ether or nitrile. That is,
Amilcinamar (also known as 2-benzylideneheptanal and α-amylcinamine aldehyde),
Amylcinnamyl alcohol (also known as 2-pentyl-3-phenylpropen-2-en-1-ol and α-amylcinamine alcohol),
Cinnamyl alcohol (also known as cinamine alcohol),
Cinamar (also known as 3-phenyl-2-propenal and cinamine aldehyde),
Citral (also known as a mixture of 3,7-dimethyl 2,6-octadien-1-al, cis and trans isomers),
Coumarin (also known as 1-benzopyran-2-one or cis-o-coumaric acid lactone),
Eugenol,
Geraniol,
Hydroxycitronal (also known as 7-hydroxycitronal or laurin),
Lyral (also known as hydroxymethyl-pentylcyclo-hexenecarboxaldehyde and 4, (4-hydroxy-4-methylpentyl) cyclohexene-3-carbaldehyde),
Isoeugenol,
Benzoyl cinnamate (INCI) (also known as benzyl 3-phenyl-2-propenoate or cinnamate),
Citronellol (also known as 3,7-dimethyl-6-octenol),
Farnesol (also known as 3,7,11-trimethyldodeca-2,6,10-trienol),
Hexylcinnamaldehyde (also known as α-hexylcinnamaldehyde),
Lilyal (rerestral, 2- (4-tert-butylbenzyl) proprionaldehyde, 4- (1,1-dimethylethyl) -α-methylbenzenepropanal, p-tert-butyl-α-methylhydrocinnamaldehyde known),
d-limonene (also known as (R) -p-menta-1,8-diene),
Linalool,
Damascon and γ-methylionone (also known as 3-methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-buten-2-one).

  In addition, the compounds can be anethole, anise oil, caraway oil, cardamom oil, carvone, coriander oil, erodisityon, ethyl vanillin, fennel oil, licorice, lavender oil, lemon oil, menthol, nutmeg oil, orange flower oil, peppermint , Rosemary oil, rose oil, spearmint oil, thyme oil, trough balsam and vanillin.

  Additional examples include angelica, bergamoten, cyclolabangular, citral, farnesal, ikema, isolauranal, ferrandrene oxime and sorbinal oxime. In particular, citral oxime can be converted to geraninitrile.

  Specifically, rilals have the following formula including double bonds:

  A cyclopropyl derivative of this compound was prepared (structure shown below).

As shown in FIG. 2, the vibrational spectra of lyral and its cyclopropanated derivative substantially overlap. The aromas of lyral and its cyclopropanated derivatives (eg, containing 1 or 2 C _1-5 alkyl groups on the cyclopropane ring) are substantially matched. Suitable odotopes of lyral include unsubstituted methyl and dimethylcyclopropyl derivatives and unsubstituted methyl and dimethylcyclopropyl derivatives in which the aldehyde is substituted with methyl ether, nitrile or acetal. )
Examples of parent ketones for these novel derivatives include α-ionone, β-ionone, γ-methylionone, iron alpha, methyl dihydrojasmonate, cis-jasmon, methyl amyl ketone, carvone, Damasenone, α-damascone, methyl-β-naphthyl ketone, casione and menthone are included.

  Still other examples include cis and trans-4-methyl-2-phenyl-2-pentenal. Replacement of the double bond with a cyclopropyl group provides a novel compound having a vibrational spectrum that substantially overlaps with the parent compound. The spectra of cis and trans-4-methyl-2-phenyl-2-pentenal are shown in FIGS. 3a and 3b, respectively.

III. Articles of Manufacture Containing Essential Oil Derivatives Derivatives described herein can be included in virtually any article of manufacture that can include a fragrance or other “parent compound” from which the fragrance is derived. . Examples include bleaching agents, detergents, flavors and fragrances, beverages including alcoholic beverages, and the like. Derivatives include soaps, shampoos, body deodorants and antiperspirants, solid or liquid detergents for textile treatment, fabric softeners, dishes for both household and industrial use or detergents for cleaning various surfaces It can be used in applications such as compositions and / or multipurpose cleaners. Other recent uses of fragrances, such as soap and shower gel fragrances, hygiene products or hair care products, and body deodorants, indoor deodorants and cosmetic formulations, and even high-grade fragrances such as perfumes and colognes As recently used, of course, the use of compounds is not limited to the above products. These uses are described in further detail below.

Fragrance composition The compound is used as a fragrance component in a single compound or a mixture thereof, preferably in the range of at least about 30% by weight of the fragrance composition, more preferably in the range of at least about 60% by weight of the composition. Can do. The compound can also be used in its pure state or as a mixture without adding any components. The odor characteristics of the individual compounds are also present in their mixtures, and mixtures of these compounds can be used as scenting ingredients. This is particularly advantageous if separation and / or purification steps can be avoided by using a mixture of compounds.

  In all listed applications, the derivatives can be used alone or in a mixture with other perfuming ingredients, solvents or adjuvants commonly used in the art. The nature and variety of these co-components need not be described in more detail here, and it is less labor intensive. Those skilled in the art will be able to select co-components according to their general knowledge and as a function of the nature of the product to be scented and the desired olfactory effect.

  These scented ingredients are generally found in a variety of chemical categories such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, sulfur and nitrogen containing heterocyclic compounds, and natural or synthetic derived aromatics. Belongs. Many of these ingredients are S. cerevisiae. Arctander's book: Perfume and Flavor Chemicals, 1969, Montclair, N .; J. et al. (U.S.) and other reference books. The entire contents or more recent versions thereof or other publications of the same type are incorporated herein by reference.

  The proportion of the derivative incorporated into the various products can vary over a wide range. This value depends on the nature of the article or product to be scented and the scent effect sought and when the compound is used in a mixture with scenting co-components, solvents or adjuvants commonly used in the industry. Depending on the nature of the co-components in a given composition.

  By way of example, the derivatives are generally present at a concentration of about 0.1 to about 10% by weight of these compounds, or more, based on the weight of the scented composition into which the compounds are incorporated. If the compounds are applied directly to the scenting of the various consumer products listed above, concentrations much lower than those mentioned above can be used.

  These compounds are relatively stable even in common aggressive media for fragrances. They are therefore used, for example, in detergents containing bleach and activators such as tetraacetylethylenediamine (TAED), hypohalites, in particular peroxide bleaches such as hypochlorite, perborate, etc. be able to. These compounds can also be used in body deodorants and antiperspirants such as those containing aluminum salts. These embodiments are described in more detail below.

Conventional detergent ingredients In addition to the derivatives described herein, the compositions herein include detergent surfactants, optionally in the treatment of substrates to be cleaned to assist or improve cleaning performance. Or one or more additional detergent ingredients, including materials for modifying the esthetics (eg, fragrances, colorants, dyes, etc.) of the detergent composition. Examples of the detersive surfactant and other detergent components are given below.

Synthetic Surfactants Non-limiting examples of detersive synthetic surfactants useful herein at levels generally from about 0.5 to about 90% by weight include conventional C _11-18 alkyl benzene sulfates ( "LAS"), and the first, branched-chain and random _{C 10 to 20} alkyl sulfates ( "AS"), the formula _{CH 3 (CH 2) X (} CH (CH 3) OSO 3 - M +) and formula CH _{3 (CH 2) Y (CH} (CH 2 CH 2) OSO 3 - M +) ( wherein, x and y are integers, x and (y + 1) are each at least about 7, preferably at least about 9 There, M is a water soluble cation, in particular such as oleyl sulfates, sodium, _{C 10 to 18} second (2,3) alkyl sulfates of the unsaturated, _{sulfates), C 10 to 18} alkyl Al Kishisurufato ( "AExS"; especially EO1~7 ethoxy _{sulfates), C 10 to 18} alkyl alkoxy carboxylates (especially EO1~5 ethoxy _{carboxylates), C 10 to 18} glycerol _{ethers, C 10 to 18} alkyl polyglycosides and These corresponding sulfated polyglycosides, as well as C _12-18 α-sulfonated fatty acid esters are included. If desired, C _12-18 alkyl ethoxylates (“AE”), including alkyl ethoxylates with so-called narrow peaks and C _6-12 alkylphenol alkoxylates (especially ethoxylates and ethoxy / propoxylate mixtures), C _12-18 betaines and sulfobetaines ( "sultaines _{(Sultaine)"),} an ordinary nonionic and amphoteric surfactants such as _{C 10 to 18} amine oxides, can also be included in the overall compositions. C _10-18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include C _12-18 N-methyl glucamide. See International Patent Application No. 9,206,154. Other saccharide-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C _10-18 N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C _12-18 glucamide can be used to reduce foaming. C _10-20 normal soaps can also be used, but synthetic detergents are preferred. Branched chain C _10-16 soaps can be used if a high degree of foaming is desired. Particularly useful are mixtures of anionic and nonionic surfactants. Other commonly useful surfactants are listed in standard reference books. See also Norris, US Pat. No. 3,664,961, issued May 23, 1972.

  Preferably, the composition containing only synthetic detergent has a detergent level of about 0.5-50%. Preferably, the soap-containing composition contains about 10 to about 90% soap.

  While the detergent compositions herein may consist solely of detersive surfactants and pro-fragrances, it is preferred that the compositions contain other ingredients commonly used in detergent products.

Builders Detergent builders can optionally be included in the compositions herein to help control mineral hardness. Both inorganic and organic builders can be used. Builders are commonly used in textile laundry compositions to help remove particulate dirt.

  The concentration of builder may vary over a wide range depending on the end use of the composition and its desired physical form. When present, the composition will generally contain at least about 1% builder. Liquid formulations typically comprise from about 5 to about 50% by weight of detergent builder, more typically from about 5 to about 30% by weight. Granular formulations typically comprise from about 10 to about 80% by weight, more typically from about 15 to about 50% by weight of detergent builder. However, lower or higher builder concentrations are not excluded.

  Inorganic or detergent builders include, but are not limited to, polyphosphates (eg tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphonates and alkali metals of phytic acid, ammonium and Phosphate builders such as alananol ammonium salts and non-phosphate builders such as silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates are included. In some cases non-phosphate builders are required.

  Organic builders suitable for use herein include Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967, and Crutfield, U.S. Pat. No. 4,144, issued March 13, 1979. Polycarboxylate builders such as those disclosed in US Pat. No. 226 and Crutfield, issued March 27, 1979, US Pat. No. 4,246,495.

Stain Remover It is desirable to use a stain remover in the laundry detergent of the present invention. Suitable soil removal agents include those described in J. J. et al. Scheibel and E.I. P. Gosselink, U.S. Pat. No. 4,968,451 (such ester oligomers include (a) ethoxylation of allyl alcohol, (b) the product of (a) and dimethyl terephthalate ("DMT") And 1,2-propylene glycol (“PG”) in a two-stage transesterification / oligomerization procedure, and (c) reacting the product of (b) with sodium metabisulfite in water Manufactured by transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"), as of December 8, 1987 US Pat. No. 4,711,730 to Gosselink et al. -Propylene / polyoxyethylene terephthalate polyester; Gosselin, Jan. 26, 1988, such as ethylene glycol ("EG"), PG, DMT and oligomers from Na-3,6-dioxa-8-hydroxyoctane sulfonate. Partially and fully anionic end-capped oligomeric esters of US Pat. No. 4,721,580; for example, DMT, Me-capped PEG and EG and / or PG, or DMT, EG and / or PG Non-capped block polyester oligo of Gosselink, U.S. Pat. No. 4,702,857, Oct. 27, 1987, manufactured from the combination of Me, capped PEG and Na-dimethyl-5-sulfoisophthalate And anionic, especially sulfoaroyl, end-capped terephthalate esters of Maladodo, Gosselink et al., Oct. 31, 1989, US Pat. No. 4,877,896 (the latter for both laundry and textile conditioning). Typical SRA 'useful in products, examples are ester compositions made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably adding PEG, eg PEG 3400 ) Etc. are included. Another preferred soil removal agent is the sulfonated end cap type described in US Pat. No. 5,415,807.

Other ingredients that may be selected The compositions herein are all well known in the art, such as enzymes, bleaches, fabric softeners, dye transfer inhibitors, foam inhibitors and chelating agents. Other ingredients may be included.

  The pH of the detergent composition for defining the detergent composition of the present invention is that measured at a detergent composition at a concentration of 1% in distilled water at 20 ° C. The detergent compositions herein have a pH of about 7.1 to about 13, more typically about 7.5 to about 9.5 for liquid detergents and about 8 to about 12 for granular detergents.

Formulations with detergents with or without conventional fragrance-making materials Although the derivatives described herein can be used alone, they can be simply mixed with basic detergent ingredients, especially surfactants. These derivatives into a three part blend of (a) a non-aromatized detergent base comprising one or more synthetic detergents and (b) one or more of the derivatives described herein. It is also desirable to do. In one embodiment, both aldehyde and acetal are present, so that the aldehyde provides the desired in-package and in-use scent (at the time of washing) while at the same time the acetal is laundered. Brings long-term fragrance to woven fabrics.

  When formulating the detergent of the present invention, a fully formulated fragrance can be prepared using a vast number of known fragrance ingredients of natural or synthetic origin. The range of natural source materials can include not only readily volatile components, but also moderately volatile and weakly volatile components. The range of synthetic source materials is apparent from the following exemplary collection: Which can be representative of all practical classes of fragrances. Natural products such as tree moss absolute, mebuki oil, citrus fruit oil (bergamot oil, mandarin oil, etc.), matrix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgren oil paraguay, mugwort oil, farnesol, geraniol, linalool, nerol, Alcohols such as phenylethyl alcohol, rosinol, cinnamin alcohol, citral, Helional (TM), [alpha] -hexyl-cinnamaldehyde, hydroxycitronal, Lilia (TM) (p-tert-butyl- [alpha] -methyldihydrocinnamaldehyde), Aldehydes such as methyl aonylacetaldehyde, allyl ionone, α-ionone, β-ionone, isoraldein (isomethyl-α-ionone) ), Ketones such as methylionone, allylic phenoxyacetate, benzyl salicylate, cinnamylpropionate, citronellyl acetate, citronellyl etoxolate, decyl acetate, dimethylbenzyl carbvinyl acetate, dimethylbenzyl carbyl butyrate, ethyl acetoacetate, Esters such as ethyl acetyl acetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, styraryl acetate, vetiberyl acetate, γ-undecalactone lactone, musk ketone, indole, p-menta-8-thiol-3-one, And various ingredients often used in the production of perfumes such as methyl-eugenol. Similarly, any conventional aromatic acetal or ketal known in the art can be added to the compositions of the present invention as an optional component of the perfume (c) normally formulated. Such normal aromatic acetals and ketals include the well-known methyl acetals and ethyl acetals, and ketals, and benzaldehyde-based acetals or ketals (including phenylethyl moieties), or the name “oxo” -Acetals and ketals of tetralin and oxo-indane "(see U.S. Pat. No. 5,084,440 issued Jan. 28, 1992, assigned to Givaudan Corp). And more recently developed chemicals. Of course, other recent synthetic chemicals can be included in perfume compositions for fully formulated detergents. These include alkyl-substituted oxo-tetralin and oxo-indane enol ethers described in U.S. Pat. No. 5,332,725, Jul. 26, 1994, assigned to Givaudan, or 1991, assigned to Givaudan. Schiff bases described in U.S. Pat. No. 5,264,615 dated 9 Dec. The pro-fragrance material is preferably added to the detergent composition of the present invention separately from the usual fragrance.

Formulations with other special purpose fragrance delivery compounds Detergents containing the derivatives described herein may optionally further comprise other known compounds that have the ability to improve the fragrance substance. May include. Such compounds include, but are not limited to, aluminum alkoxides such as isobutyl aluminum diferranlate described in US Pat. No. 4,055,634, or US Pat. Nos. 3,947,574 and 3,779, Known titanate esters and zirconate esters or oligoesters of aromatic materials, such as those described in US Pat. No. 932, are included. The entire contents of each of these are incorporated herein by reference. If such organoaluminum, organotitanium or organozinc derivatives are used, they can be mixed in the formulations of the present invention at concentrations known in the art.

Beverage compositions The improved flavors described herein can be incorporated into beverages to impart a variety of flavors to the beverage. The preferred flavor is lemon, but further includes flavors such as rose, cinnamon, and lime. The beverage composition may be a cola beverage composition and may be a coffee, tea, dairy beverage, fruit juice water, citrus beverage, lemon-lime beverage, beer, malt beverage or other flavored beverage. Good. The beverage may be in liquid form or powder form.

  The beverage composition comprises one or more flavoring agents; artificial colorants, vitamin additives, preservatives, caffeine additives, water, acidulants, thickeners, buffers, emulsifiers and / or fruit juice concentrates You can also.

  Artificial colorants that may be used include caramel color, Yellow No. 6 and Yellow No. 5. Useful vitamin additives include vitamin B2, vitamin B6, vitamin B12, vitamin C (ascorbic acid), nicotinic acid, pantothenic acid, biotinic acid and folic acid. Suitable preservatives include sodium benzoate or potassium benzoate. Salts that may be used include sodium chloride, potassium chloride and magnesium chloride. Examples of emulsifiers are gum arabic and high purity rubber, and a useful thickener is pectin. Suitable acidulants include citric acid, phosphoric acid and malic acid, and possible buffering agents include sodium citrate and potassium citrate.

  In one embodiment, the beverage is a carbonated cola beverage. The pH is generally about 2.8 and a flavorant concentrate (22.22 ml) containing the following ingredients to make a syrup for these compositions: one or more of the derivatives described herein 80% phosphoric acid (5.55 g), citric acid (0.267 g), caffeine (1.24 g), artificial sweetener, sugar or corn syrup (for seasoning, depending on actual sweetener) and Potassium citrate (4.07 g) can be used. The beverage composition can be prepared, for example, by mixing the syrup with carbonated water at a ratio of 50 ml of syrup to 250 ml of carbonated water.

  In other embodiments, the beverage is a beer or malt beverage. Preferred flavoring agents for beer and malt beverages include lemon, lime and lemon-lime. A flavoring agent is a citral derivative in which one of both double bonds is substituted with a cyclopropane group, wherein the cyclopropane group is independently unsubstituted, or one or two alkyl or substituted It is advantageous to include derivatives that may contain alkyl groups, preferably methyl groups. The amount of flavoring agent can be adjusted according to taste.

Oral delivery products Flavored food and pharmaceutical compositions containing one or more of the derivatives described herein can also be prepared. Derivatives can be incorporated into conventional food products using techniques well known to those skilled in the art. Alternatively, the derivative can be incorporated into polymeric particles which are then dispersed in and / or on the orally deliverable matrix material, which is usually a solid or semi-solid substrate. When used in a chewable composition, when the composition is chewed, the derivative is released into the orally deliverable polymeric matrix material and retained in the mouth, thereby prolonging the flavor of the composition. Make it. In the case of dry powders and mixtures, a flavor is provided when the product is consumed, or the flavor is released into the matrix material when the composition is further processed. When combining two flavoring agents with polymeric particles, the relative amounts of additives can be selected to allow simultaneous release of the compound and exhaust the compound.

  In one embodiment, the flavored composition includes an orally deliverable matrix material, i.e., polymeric particles, that individually define a network of internal pores and are non-degradable in the gastrointestinal tract. Included are a number of water-soluble polymeric particles dispersed in a possible matrix material, and one or more derivatives described herein trapped in an internal pore network. The derivative is released when the matrix is chewed and dissolved in the mouth or upon further processing selected from the group consisting of liquid addition, dry blending, stirring, mixing, heating, baking and cooking. Orally deliverable matrix materials include rubber, latex material, crystallized sugar, amorphous sugar, fondant, nougat, jam, jelly, paste, powder, dry blend, dehydrated food mix, baked goods, butter, bread dough, Selected from the group consisting of tablets and lozenges.

Chewing gum Unflavored gum base can be mixed with the citral or other suitable derivatives described herein to achieve the desired flavor concentration. Generally, the blade mixer is heated to about 110 F (43 ° C.), the gum base is preheated to soften, and then the gum base is added to the mixer and mixed for about 30 seconds. The flavored derivative is then added to the mixer and mixed for an appropriate amount of time. The gum is then removed from the mixer and rolled over wax paper while warm to the thickness of the stick.

Sustained Release Formulation In one embodiment, the derivatives described herein can be incorporated into a system that can release fragrance in a controlled manner. These include substrates such as indoor deodorants, laundry detergents, fabric softeners, deodorants, lotions and other household items. The fragrance is generally a derivative of one or more fragrances described herein, each present in a different amount. U.S. Pat. No. 4,587,129 describes a method for preparing gel articles containing up to 90% by weight of fragrance or perfume oil. The entire contents of which are incorporated herein by reference. These gel articles are prepared from a polymer having hydroxy (lower alkoxy) 2-alkenoate, hydroxy (lower alkoxy) lower alkyl 2-alkenoate or hydroxypoly (lower alkoxy) lower alkyl 2-alkenoate, and a polyethylene unsaturated crosslinker. be able to. These materials have continuous sustained release properties, i.e., release fragrance components over a long period of time. It is advantageous to modify all or part of these derivatives containing aldehyde groups to include acetal groups. This acetal group can hydrolyze to produce an aldehyde compound while providing a long-term fragrance release to the formulation.

  While this has disclosed the subject matter of the present invention, it should be apparent that many variations, substitutions and variations of the present invention are possible in light of it. It should be understood that the invention can be practiced otherwise than as specifically described. Such modifications, substitutions and variations are intended to be within the scope of this application.

It is a figure which shows the vibration spectrum of the cyclopropyl derivative of rose oxide. It is a figure which shows the vibrational spectrum of the cyclopropyl derivative | guide_body of a linalool. It is a figure which shows the vibrational spectrum of the cyclopropyl derivative of limonene. It is a figure which shows the vibrational spectrum of the cyclopropyl derivative of ionone. It is a figure which shows the vibration spectrum of a lyral cyclopropyl derivative. It is a figure which shows the vibrational spectrum of cis-4-methyl-2-phenyl-2-pentenal. It is a figure which shows the vibrational spectrum of trans-4-methyl-2-phenyl-2-pentenal. It is a figure which shows the typical table | surface of the aromatic chemical | drug | medicine which can be modified using the chemistry demonstrated in this specification.

Claims (26)

At least one double bond in the fragrance is substituted with a three-membered ring, said three-membered ring comprising two carbons from which the double bond is derived, each of which is oxygen, sulfur or C ( R) is bonded to _two groups,
R is independently H, C _1-5 alkyl or C _1-5 substituted alkyl;
The substituent on the substituted alkyl group contains at least one double bond selected from the group consisting of halo, hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano, sulfonic acid, urea and thiourea A derivative of aromatic chemicals.   The derivative according to claim 1, wherein at least one R is methyl.   A derivative of a fragrance chemical comprising at least one double bond in which at least one double bond in the fragrance chemical is replaced by a thioether bond.   A derivative of a fragrance comprising at least one phenyl ring in which at least one phenyl ring in the fragrance is substituted with a thiophene ring.   The fragrance chemical comprises at least one aldehyde group, and at least one aldehyde group in the fragrance chemical is further substituted with a nitrile, methyl ether, ester or acetal group. Derivative.   A composition comprising a compound according to any of claims 1 to 6 together with other perfuming ingredients, solvents or adjuvants commonly used in the fragrance manufacturing industry.   8. A composition according to claim 7, wherein the compound is present in an amount of at least 30% by weight.   8. A composition according to claim 7 wherein the compound is present in an amount of at least 60% by weight of the compound according to any of claims 1-6.   A scented composition or a scented article containing the compound according to any one of claims 1 to 6 or a mixture of compounds as a scented component.   11. A fragrance composition according to claim 10 wherein the compound or mixture of compounds is present in admixture with other fragrance ingredients, solvents or adjuvants commonly used in the art.   Perfume or cologne, soap, bath or shower gel, shampoo or other hair care product, cosmetic formulation, body deodorant or antiperspirant, indoor deodorant, textile detergent or softener or general household cleaning 11. A scented article according to claim 10 in the form of an agent.   A body deodorant agent or an antiperspirant containing the compound according to any one of claims 1 to 6 or a mixture of compounds as a scenting component.   14. A body deodorant or antiperspirant as claimed in claim 13 wherein the compound or mixture of compounds is present in admixture with other perfuming ingredients, solvents or adjuvants commonly used in the art.   A detergent containing the compound according to any one of claims 1 to 6 or a mixture of compounds as a scenting component.   16. A detergent according to claim 15 wherein the compound or mixture of compounds is present in admixture with other perfuming ingredients, solvents or adjuvants commonly used in the art.   A bleaching composition comprising the citral derivative according to claim 1.   A beverage comprising the citral derivative according to any one of claims 1 to 6.   19. A beverage according to claim 18 selected from the group consisting of beer, malt liquor, lemonade and cola.   A flavored oral delivery product comprising the citral derivative of claim 1.   An improvement, enhancement or modification of the scent of a scented composition or scented article comprising adding an effective amount of a compound or mixture of compounds according to any of claims 1 to 6 to the composition or the article. Way for.   The method of claim 21, wherein the compound or mixture of compounds is present in admixture with other perfuming ingredients, solvents or adjuvants commonly used in the art.   The method of claim 21, wherein the compound is present in an amount of at least 30% by weight.   Essential oils are Angelica, Allepurin, α, β-Apocitronal, Bergamoten, Pyrotelenne, Camphoren, Citronellal, Citral, Kryzanthem, Cyclocitral, Cyclolabanglar, Faranar, Farnesal, Isolauranal, Ikema, Miltenal, Ferrandren, Safra The composition according to any one of claims 1 to 6, which is selected from the group consisting of naloxime and sorbinal oxime.   The essential oils are amylcinamarl, amylcinnamyl alcohol, cinnamyl alcohol, cinamar, citral, coumarin, eugenol, geraniol, hydroxycitronellal, lyral, isoeugenol, benzoylcinnamate, citronellol, farnesol, hexylcinnamaldehyde, lyrial, d- The composition according to any one of claims 1 to 6, which is selected from the group consisting of limonene, linalool, demascanone and γ-methylionone.   Essential oils are anetole, anise oil, caraway oil, cardamom oil, carvone, coriander oil, yerba santa, ethyl vanillin, fennel oil, licorice, lavender oil, lemon oil, menthol, nutmeg oil, orange flower oil, peppermint, rosemary oil, The composition according to any one of claims 1 to 6, wherein the composition is selected from the group consisting of rose oil, spearmint oil, thyme oil, trout balsam and vanillin.   The composition according to any one of claims 1 to 6, wherein the essential oil is selected from the group consisting of lyial, cyclamenaldehyde, boujunal and citral.

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